Organic polysulfides



Patented Jan. as, 1947 2,415,002

UNITED STATES PATENT" OFFICE oaomc rousunrmns Herman A. Bruson, Philadelphia, Pa., asaignor to The Resinous Products a Chemical Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application January 16, 1945, Serial No. 573,141

'1 Claims. (01. 260-808) This invention relates to organic polysulfldes alicyclic group, such as the dihydronorpolycyclohaving the formula: pentadienyl, such hydrocarbon substituents are not required for low temperature oils.

J i Typical highly desirable polysulfldes obtainable according to this invention are the iollow- R-o-oH,-oH-(ooH0H=) ing:

i x 1. on, em wherein R is a carbocyclic nucleus, X is a memcm-o-Oo-om-om-srontom-oOo-omber of the group consisting of hydrogen and lower H alkyl groups, y is a number from zero to two, inclusive, and n is a number from two to four, a OHPCH, inclusive.

An object of this invention is to provide a new 4) group of organic polysulfldes of the above foron, om-o I 2 mula, possessing a low degree oi. color, which can be added to lubricating oils to enhance their a. can CtHu properties, more specifically for improving their resistance to oxidation, for reducing their corro- 0oH|-CHi-si-cH,-cHi-0 sion of silveror copper-containing bearings, and 2 o'mFAmyl 150mm for improving their lubrication at increased or extreme pressures and high temperatures. These oyflmm new polysulfides are remarkably free from skin irritation and can be used in cutting and boring oils -on lathe and bench operations where the Y 2 lubricants may come in contact with an operator's 5. hands. They can also be used for preparing wiredrawing oils and gear oils where extremely high I: D ]I local pressures and temperatures are encountered. Q I 15m (1110 The new compounds of this invention are ob- 0 4 tainable by reacting a Halide of the formula. go GHHLCH 03.1%.

ROCHg-CH O-CH--CH: 01

I l H: H: 2 X X 1 on on wherein R, X, and 1 have the significance meng r tioned above, with a solution of an alkali metal Cami-c polysulflde, advantageously in a, mutual solvent cm-o l 2 such as alcohol. 8'

For use in petroleum oils, it is desirable that on. CHI the above organic polysuliides be soluble in the CH 43 CH CH oils to the extent of from about 0.5% to 10%, the H H I 2 optimum amount depending upon the character of the oil used, i. e., whether paraflinic or naph- 9.

thenic, the percentage of sulfur present in the organic polysulflde, and the use to which the oil is to be subjected. In general, it has been found 45 2 highly desirable to have present a hydrocarbon substituent, such as an alkyl or cycloaikyl group, O H Dodecylisomors attached to the carbocyclic nucleus, R, to enhance the oil solubility of the above polysulfldes, par ticularly when R is, for example, an aromatic v E ring. In order to prevent separation of these og (:{L cg,

organic polysulfldes from petroleum oils at low temperatures, it is desirable that the substituent when c'mws alkyl group of a benzenoid nucleus contain at least four carbon atoms, although when R is an on rmuse in naphthenic type petroleum oils, the

presence of an alkyl or cycloalkyl group is not as important for solubility and, consequently, com

pounds in which R is unalkylated can be used.

For this purpose, the following type compounds come within thepurview of this invention:

o-om-cn-o-cir-cm Hi a l 80-01mm I Furthermore, where extremely high pressures are encountered, as in the case of worm and gear oils, it is advantageous that one or more halogen atoms be present in the aromatic nucleus R. For this purpose, the following type compounds come within the purview of this invention:

on.- o-omcm-o-cmcm H HI 2 on. m Br cm-o-cHroGo-cmcBro-omen. s.

CH: CHsCHr- O-CHaCH: s

In practicing this invention, compounds in which R is a benzene or naphthalene ring which can be unsubstituted. or which can be nuclearly substituted with hydrocarbon groups (alkyl, aryl, cycloalkyl) or with halogen groups, are to be considered within its scope. Furthermore, X can be a short chain alkyl group other than methyl,

such as ethyl, propyl, or butyl.

In preparing the organic polysulfides of this invention, a solution of an alkali polysulfide is prepared by dissolving'flowers of sulfur in, for example, an aqueous sodium sulfide solution. The amount of sulfur dissolved is selected so that the solution of sodium polysulfide obtained contains one or more atoms of sulfur per atom of sodium. This solution is reacted in alcoholic solution at the boiling point thereof with two molecular equivalents of the halide having the formula:

catalysts.

pentadiene in the presence of BF: with ethylene chlorohydrin or diethylene glycol chlorohydrin, or by reacting Diels-Alder type addition products 01 olefins. and cyclopentadiene with ethylene chlorohydrin or diethylene chlorohydrin in the presence of sulfuric acid or phosphoric acid as Upon heating carbocyclic oxyaliphatichalides of this type with sodium polysulfldes having from one to two sulfur atoms per atom of sodium, the following reaction occurs: J

wherein n is equal to two to four, inclusive.

The new organic polysulfides obtained in this way are, after being washed and dried in vacuo, pale yellow to deep amber-colored thick oils. A few of them are waxy solids. They are practically non-volatile and almost inodorous when purified by warming with absorbent charcoal. They dissolve readily in aromatic hydrocarbons and also dissolve in other types of hydrocarbons, particularly if R is hydrocarbon substituted, and are not afiected by steam, dilute acids, or alkalies. Furthermore, in contrast to monothioethers, they are not readily oxidized to form sulfoxides or suifones and are, therefore, extremely stable in lubricating oils with which they may be mixed. It should be also noted that the mono-thioethers are lacking in those properties which render the polysulfides of this invention useful.

The following examples illustrate this invention:

Example 1 To a stirred mixture of '72 grams of powdered sulfur and 180 grams of sodium sulfide crystals (Na2S.9HzO) at 0., there was gradually added a solution of 375 grams of ethanol and 156.5 grams of fi-phonoxyethyl chloride. The mixture was then boiled under reflux for seven hours with constant stirring. The reaction product was poured into water and the oil layer separated and washed several times with warm water. The washed oil was dried in vacuo at 90-95 C. The residue was an amber-colored oil which, on standing, become a waxy solid. Its com-position corresponds to the formula:

The procedure described in Example 1 was applied to 170.5 grams of fl-(ortho-cresoxy) -ethyl chloride in place of the p-phenoxyethyl chloride. The product was a.v pale amber-colored oil corresponding to the formula:

Example 3 v A mixture of 200 grams of fi-(phenoxyethom) ethyl chloride,

CeH5O-CH2CHa-O-CH2CH2C1 375 grams of ethanol was mixed with a solution of Heidi prepared from 180 grams of NaaSJiHzO and 72 grams of sulfur and boiled for seven hours under reflux with continuous stirring. The prod not was poured into water and the oil layer separated and washed several times with hot water. Theresidual oil, after being dried in vacuo,

was an ambercolored liquid corresponding in composition to, the formula;

[CoHr-Q-CHICHa-OllHiCHflz-Si Example! A mixture of 114 grams oi"p+(phenoxy-isopropoxy) -isopropyl chloride, I

II and 190 grams of ethanol was boiled under reflux forsix hours with a solution of Nazsi prepared from 90 grams of NazS.9H2O and 36 grams of sulfur. The product was isolated by pouring it into water and washing and drying of the separated oil. It formed a pale yellow liquid having the folnula: I

[cinr-o-cm-cno-cncni]si H: 41H: 8 ExampleS A. mixture of 90 grams of Na2S.9HaO, 36 grams of sulfur, 190 grams of ethanol, and 125 grams of fi-naphthoxyethoxy ethyl chloride was boiled under reflux for six and one-half hours with rapid stirring. The product was poured into water, washed, and dried in vacuo. The product was a thick oil having the formula:

Example 6 A mixture of 144 grams of NaeS.9HzO and 19.2 grams of flowers of sulfur was heated for fifteen minutes until a clear solution was obtained. To this was added 300 grams of ethanol and25o grams of p-e,;y, stetramethylbutylphenoxyethoxyethyl chloride:

CH: CHI

Ha CHa The mixture was stirred and boiled under reflux for seven hours. The product was poured into water and the oil layer separated, washed, and dried in vacuo at 95 C. The residual compound was a pale yellow oil having the formula:

Example 7 The procedure of Example 6 was repeated except that 38.4 grams of flowers of sulfur was used instead of 19.2 grams. The product was a pale yellow oil having the formula:

Example 8 The procedure of Example 8 was repeated except that 57.6, grams of flowers of sulfur was used instead of 19.2 grams. The product was a pale yellow viscous oil having the formula:

(a) To mifi turegr izsllmms(vim cyclopentadiene and" 161' 8 1ns}.of.ethylene Sch rohydrin there .was "gr uallylq added "2 8 are of bore .triduormesd ih r ether.eradicatin at 60 C. The .inixtu stirred'at 16 0? "Cgj fo H was washed 'with. .w&fie and with' soda "solutionLahd. distilled in vacuo, j to give 250 grams of fi-chloroethoxydlhydronordi'j 1 four hours .long'er'..j th

m cyclopentadiene:

20 28.8 grams of sulfur'was heated until the sulfur dissolved. To'this solution was added 350 grams of ethanol and 250 grams of the 'chloroethylether from (a) above,-and the mixture was stirred and boiled for seven hours under reflux. The product was poured into hot water and the oil layer was separated, washed, and dried. It was apaie amber-colored oil having the formula:

[C1oH1r-O-CH|CH1]r- -s2 where CroHra represents the dihydronordicyciopentadienyl nucleus as above.

(c) The procedure in (b) above was modified by using 57.6 grams of sulfur instead of 28.8 grams. The product obtained was a. thick oil having the formula:

(d) The procedure in (b) above was modified by using 86.4 grams of sulfur instead of 28.8 grams. The product obtained was a thick oil having the formula:

These polysulfides are extremely soluble in refined Pennsylvania lubricating oils and can be used in amounts up to 10% on the weight of such oils to improve their lubricating properties for wire-drawing and lathe-cutting operations.

Example 10 To a stirred solution of 60 grams of ethylene chlorohydrin and five grams of BFh.O(C2I-Is)a heated to 70 0,, there was gradually added 91 grams of the Diels-Alder addition product of indene and cyclopentadiene, namely, .1,4-endomethylene tetrahydrofluorene, having the for-.

mula:

H l H: n C

Twomolecular equivalents of the above ether chloride dissolved in an equal volume of ethanol was boiled for seven hours on a steam bath, with stirring, with a product obtained from one molecular equivalent of NB2S.9H2O and three atomic equivalents of sulfur. The reaction mixture was poured into water and the oil layer was separated, washed with hot water, and dried in vacuo. The

final product was an amber-colored thick-oil havving ether chlorides were reacted with alcoholic aqueous solutions of NazSa, NazSa. and Naast to yield the corresponding organic polysulfldes:

p'-Tert.-butyl-phenoxyethoxy ethyl chloride p-Tert.-amyl-phenoxyethoxy ethyl chloride o-Cyclohexyl-phenoxyethoxy ethyl chloride o-Dodecyl-phenoxyethoxy ethyl chloride 3,5-dimethyl-phenoxyethoxy ethyl chloride 2,6-dichloro 4 p-tert. amylphenoxyethoxy ethyl chloride (12) (c) (d) (e) (f) ride I 2-tert.-buty1-1-naphthoxyethoxy ethyl chloride p-Tert.-octylphenoxy ethoxy ethoxy ethyl chloride p-Tert.-octylphenoxy isopropoxy isopropyl chloride 2-bromo-4-p-tert.-octylphenoxyethyl chlo- 8 I claim: Y 1. As a new compound, on organic polysuliide having-the formula:

wherein R, is a-Jicarbocyclic hydrocarbon having five to six carbon. atoms in any single The products obtained were in each case thick oils which were soluble in petroleum products and effective therein as additives for improving properties, as described above. They may be used as the sole additive or they may be used in conjunction with other additives, including other antioxidants, pourpoint depressors, viscosity-index improvers (typified by lauryl or cetyl polymethacrylates), etc., or with metal soaps in the preparation of greases.

The preferred sub-class of compounds of this invention may be represented by the formula:

wherein R is an aromatic nucleus, 11' is a number from one to three, inclusive, and n is a number from two to four, inclusive. It may be a phenyl nucleus, particularly one having a hydrocarbon substituent.

cycle, X is a member of the group consisting of hydrogen and lower alkyl groups. 1! is a number from zero to two, inclusive, and n is a number from two to four. inclusive.

2. As a new compound. on organic polyauliido having the formula:

wherein R is an aromatic ring of the banana series. X is a member of the group consisting of hydrogen and lower alkyl groups, and n is a number from two tofour, inclusive.

3. As a new compound. an organic polysulflde having the formula:

[mo CHzCHzhlr-S- wherein R is an alkylated phenyl groumy' is a number from one to three, inclusive, and n is an integer from two tofour, inclusive.

4. As a new compound, an organic polysulfld'e having the formula:

ca-o-cmcm-o-cmcnm s1.

wherein R is an alkylated benzene ring and n is a number from two to four, inclusive.

5. As a new compound, an organic polysulflde having the formula:

F CH3 CH3 I CHa- -CHr-(BOOCH2CHr-O-CH1CH: I a 41H:

having the formula:

7. As a new compound, an organic polysulilde having the formula:

- CH: CH!

HI Kl HERMAN A. BRUSON.

15. As a new compound, an organic polysulflde I 

